CN102005303B - Method for preparing SiO2-modified ZnO nano-porous thin film composite electrode - Google Patents

Method for preparing SiO2-modified ZnO nano-porous thin film composite electrode Download PDF

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CN102005303B
CN102005303B CN 201010575239 CN201010575239A CN102005303B CN 102005303 B CN102005303 B CN 102005303B CN 201010575239 CN201010575239 CN 201010575239 CN 201010575239 A CN201010575239 A CN 201010575239A CN 102005303 B CN102005303 B CN 102005303B
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zno nano
zno
combination electrode
thin film
sio
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CN102005303A (en
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张跃
秦子
黄运华
廖庆亮
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention belongs to the technical field of nano-materials, and relates to a method for preparing a SiO2-modified ZnO nano-porous thin film composite electrode, which is characterized in that a ZnO nano-particle porous thin film is used as the base layer of the composite electrode; a spin-coated silicon oxide sol protective layer is selected to improve the corrosion resistance of the ZnO nano-particle porous thin film in an acid dye for the stability of a dye-sensitized solar cell. The coating layer number, the sintering time and the concentration of sole are adjusted so as to reasonably control the thickness of a silicon oxide thin film coat, thereby obtaining the composite electrode with strong corrosion resistance and excellent performance. In the invention, process parameters can be adjusted according to different sensitized conditions so as to obtain the SiO2-ZnO nanoparticle porous thin film composite electrode with strong acid resistance in the process of sensitization and optimal electrode performance. The production process has the advantages of high efficiency, low cost and the like, and is suitable for future large-scale production.

Description

SiO 2The preparation method of the ZnO nano-porous film combination electrode of modifying
Technical field
The invention belongs to technical field of nano material; Particularly provide a kind of silica decorative layer that adopts to prevent the method that the Zinc oxide nanoparticle porous film electrode is corroded and damages in carrying out the dye sensitization process, related to the preparation method of the compound electric anode of a kind of DSSC.
Background technology
Exploitation cheapness, cleaning, environmental friendliness and reproducible new forms of energy have become a focus in current research field.Solar energy is the abundantest regenerative resource of resource, but as a kind of clean energy resource of continuous utilization, huge Application and Development potentiality is arranged.At present, silicon solar cell has been widely used in fields such as space flight, communication, traffic.Although the transformation efficiency of this kind battery is high, its manufacturing process is complicated, material requirements is harsh and cost an arm and a leg.And DSSC becomes a big hot topic field of Recent study with its higher transfer ratio, advantage such as cost is low, manufacture craft is simple.ZnO has suitable energy gap, big specific area to photoetch stability and good electron transmission property, and is employed as light anode material that too can dye-sensitized cell.Although at present the transformation efficiency based on the DSSC of ZnO nano material still is lower than based on TiO 2Particle too can battery.But the mobility of electronics is high among the ZnO, can reduce the loss of electronics in communication process, and the potential of very big raising battery light energy transformation efficiency is arranged.Simultaneously, the ZnO preparation of nanomaterials is simply various, can obtain large tracts of land, the various ZnO nanostructure (as: nano particle, rod, line, array, four pins, band, ring, comb etc.) of pattern through the control synthetic reaction.This appearance structure not only helps the structure of light anode is optimized, and is expected to further reduce the battery cost.(Z.Qin，Q.L.Liao，Y.H.Huang，L.D.Tang，X.H.Zhang，Y.Zhang，Mater.Chem.Phys.123(2010)811；N.Ye，J.J.Qi，Z.Qi，X.M.Zhang，Y.Yang，J.Liu，Y.Zhang，J.Power?Sources?195(2010)5806)
At present, concerning based on the DSSC of ZnO nanometer particle film, its transformation efficiency still is lower than TiO 2Nanocrystalline DSSC.Its main restraining factors are energy level and the energy level match condition of ZnO material and the adsorption binding energy power between them of dyestuff.The dyestuff that commercialization is at present used is one type of photosensitive dye of superior performance mostly as many pyridines organometallic complex (as: N3, N719 etc.) of ruthenium.Yet it is acid that the dyestuff of this type becomes in solution, not only can cause corrosion damage and particle agglomeration to the surface of ZnO nano material.In aggregation procedure, can produce a large amount of Zn 2+/ dye complex, they seriously hinder the injection efficiency of electronics.Therefore, improve based on the continuation of the transformation efficiency of the DSSC of ZnO nano particle porous film electrode and received certain restriction.(M.Law，L.E.Greene，A.Radenovic，T.Kuykendall，J.Liphardt，P.D.Yang，J.Phys.Chem.B?110(2006)22652；S.H.Kang，J.Y.Kim，Y.Kim，H.S.Kim，Y.E.Sung，J.Phys.Chem.C?111(2007)9614；X.J.Wang，M.K.Lei，T.Yang，L.J.Yuan，J.Mater.Res.18(2003)2401.)。
Summary of the invention
The object of the invention is to provide a kind of method that adopts the silica decorative layer to improve Zinc oxide nanoparticle porous film electrode anticorrosive damage ability in dyestuff soaks, and prepares a kind of SiO that is applicable to the DSSC high stability 2-ZnO nano particle porous membrane combination electrode.The anti-dyestuff corrosivity of combination electrode of this method preparation is strong, and its production technology have efficient height, cost low, be suitable for many advantages such as following large-scale production.
The present invention proposes a kind of in the dye sensitization process the strong SiO of corrosion resistance 2The preparation method of-ZnO nano particle porous membrane combination electrode.Adopt the knife coating method on conductive substrates, to prepare the ZnO nanometer particle film of porous; Utilize spin coating method at ZnO nanometer particle film surface recombination one deck SiO 2Film.Can obtain the SiO that acid resistance is strong in activation process, electrode performance is good to different sensitization condition adjusting process parameters 2-ZnO nano particle porous membrane combination electrode.Concrete processing step is following:
1. after ZnO powder fully being ground 30 minutes to 1 hour, be chosen in more than 400～600 degrees centigrade of following heat treatment half an hour, naturally cool to room temperature at last.
2. the ZnO powder of the said processing of step 1 and ethyl cellulose, terpinol are mixed in 2: 1: 8～1: 1: 5 mass ratio and are prepared into slurry in the absolute ethyl alcohol.Dispersed with stirring was handled 0.5～1 hour in the ultrasonic oscillation device.Be placed on the heating furnace subsequently and heat, and constantly stirred 20～30 minutes, until forming the suitable thick shape ZnO nano pulp of viscosity.
3. with ZnO nano pulp uniform spreading on conductive substrates, leave standstill homogenizing 15 minutes, calcined 0.5～1 hour down at 400～800 ℃ then, can obtain ZnO nano particle porous film electrode.The operation of this step of repetition can be selected repeatedly, the ZnO nano particle porous film electrode of desired thickness can be obtained.
4. the silica content in the silica hydrosol is adjusted in the scope of 10～26wt%, sonicated obtained the suitable colloidal solution of viscosity after 15 minutes.The colloidal solution after sonicated of getting 0.1 milliliter drips in the ZnO nano particle porous membrane surface that has made.Rotary speed is set to 1000 rev/mins of low speed, 3000 rev/mins of high speeds.After leaving standstill 10 minutes,,, just can obtain uniform colloid coated electrode top gear rotation 10～20 seconds respectively low or first gear rotation 5～10 seconds.According to the parameter request of different sensitization conditions, time coating of optional majority.
6. the good electrode of the said spin coating of step 4 is put into box type furnace,, can make SiO 400～800 ℃ of interval heat treatments 0.5～1 hour 2-ZnO nano particle porous membrane combination electrode.
Compared with prior art, the prepared preparation method based on the dye sensitization solar battery electrode of ZnO nano particle of the present invention has following advantage:
1. the SiO of spin-coating method preparation 2Protective layer has improved the antiacid corrosivity when ZnO nano particle porous film electrode soaks in acid dyes, effectively suppressed the reunion between the ZnO particle and influenced the Zn of electron injection efficiency 2+The generation of/dye complex.
2. adopt spin coating sol method technology simple, can obtain surface SiO uniformly 2Film coating.
3. can rationally control SiO through the adjustment that colloidal sol is applied the number of plies, sintering number, concentration 2The thickness of film coating obtains the combination electrode of the strong and excellent performance of corrosion resistance.
4. utilize this SiO 2The sensitization performance of the DSSC of-ZnO nano particle porous membrane combination electrode assembling is improved.
Description of drawings
Fig. 1 adopts the ZnO nano particle porous membrane surface topography stereoscan photograph of knife coating preparation for the present invention.Many, the even particle size of gained film hole.
Fig. 2 adopts the SiO of spin coating method preparation for the present invention 2The ZnO nano particle porous membrane combination electrode side pattern electromicroscopic photograph of modifying.
Fig. 3 is the SiO of the present invention's preparation 2The EDS energy spectrum analysis of the ZnO nano particle porous membrane combination electrode of modifying.
Fig. 4 utilizes the SiO of preparation for the present invention 2The battery performance curve of-ZnO nanorod array combination electrode after the different sensitization times of process.This performance curve has explained that the combination electrode that the present invention obtains has very excellent corrosion-resistant damage performance.
Embodiment
Below in conjunction with instance technical scheme of the present invention is further specified:
Instance 1
1. ZnO powder was fully ground 45 minutes, 500 degrees centigrade of following heat treatments 45 minutes, naturally cool to room temperature at last then.
2. ZnO powder (4g), terpinol (18mL), ethyl cellulose (2.0g), the alcohol (50mL) with above-mentioned processing is mixed with form slurry.Elder generation's ultrasonic oscillation stir process 30 minutes.Be placed on the heating furnace subsequently and heat, and constantly stirred 20～30 minutes, until forming thick slurry.
3. the ZnO nano pulp evenly is coated on the FTO electro-conductive glass, dry back sintering 1 hour in 450 ℃ box type furnace takes out behind the natural cooling, can obtain the ZnO nano particle porous film electrode that thickness is about 10 microns.
4. get the silica sol that concentration is about 11～13wt%, sonicated obtained the suitable colloidal solution of viscosity after 15 minutes.Drawing above-mentioned alumina sol with dropper drips respectively in the ZnO nano particle porous film electrode surface that has made.Subsequently 1000 rev/mins low or first gear rotation 10 seconds, 3000 rev/mins of top gears rotations 15 seconds.Can on ZnO nano particle porous membrane, obtain the combination electrode of the colloid layer of uniform surface.
5. the combination electrode that above-mentioned spin coating is good is put into box type furnace, 500 ℃ of following annealing in process 45 minutes, promptly obtains SiO after the cooling 2-ZnO nano particle porous membrane combination electrode.
Instance 2
1. ZnO powder was fully ground 50 minutes, 450 degrees centigrade of following heat treatments 30 minutes, naturally cool to room temperature at last then.
2. ZnO powder (2g), terpinol (9mL), ethyl cellulose (1.0g), the alcohol (50mL) with above-mentioned processing is mixed with form slurry.Elder generation's ultrasonic oscillation stir process 30 minutes.Be placed on the heating furnace subsequently and heat, and constantly stirred 20～30 minutes, until forming thick slurry.
3. the ZnO nano pulp evenly is coated on the aluminium flake, dry back sintering 1 hour in 450 ℃ box type furnace takes out behind the natural cooling, can obtain the ZnO nano particle porous film electrode that thickness is about 10 microns.
4. get the silica sol that concentration is about 11～13wt%, sonicated obtained the suitable colloidal solution of viscosity after 15 minutes.Drawing above-mentioned alumina sol with dropper drips respectively in the ZnO nano particle porous film electrode surface that has made.Subsequently 1000 rev/mins low or first gear rotation 10 seconds, 3000 rev/mins of top gears rotations 15 seconds.Can on ZnO nano particle porous membrane, obtain the combination electrode of the colloid layer of uniform surface.
5. the combination electrode that above-mentioned spin coating is good is put into box type furnace, 500 ℃ of following annealing in process 45 minutes, promptly obtains SiO after the cooling 2-ZnO nano particle porous membrane combination electrode.
Instance 3
1. ZnO powder was fully ground 40 minutes, 450 degrees centigrade of following heat treatments 30 minutes, naturally cool to room temperature at last then.
2. ZnO powder (2g), terpinol (9mL), ethyl cellulose (1.5g), the alcohol (100mL) with above-mentioned processing is mixed with form slurry.Elder generation's ultrasonic oscillation stir process 30 minutes.Be placed on the heating furnace subsequently and heat, and constantly stirred 20～30 minutes, until forming thick slurry.
3. the ZnO nano pulp evenly is coated on the stainless steel substrates, dry back sintering 1 hour in 450 ℃ box type furnace takes out behind the natural cooling.Repetitive coatings 2 times can obtain the ZnO nano particle porous film electrode that thickness is about 30 microns.
4. get the silica sol that concentration is about 11～13wt%, sonicated obtained the suitable colloidal solution of viscosity after 15 minutes.Drawing above-mentioned alumina sol with dropper drips respectively in the ZnO nano particle porous film electrode surface that has made.Subsequently 1000 rev/mins low or first gear rotation 10 seconds, 3000 rev/mins of top gears rotations 15 seconds.Can on ZnO nano particle porous membrane, obtain the combination electrode of the colloid layer of uniform surface.
5. the combination electrode that above-mentioned spin coating is good is put into box type furnace, 600 ℃ of following annealing in process 45 minutes, promptly obtains SiO after the cooling 2-ZnO nano particle porous membrane combination electrode.

Claims (4)

1. SiO 2The preparation method of the ZnO nano-porous film combination electrode of modifying is characterized in that step of preparation process is:
A. after ZnO powder fully being ground, put into heating furnace, handled 0.5～1 hour down at 400～600 degrees centigrade;
B. the ZnO powder of above-mentioned processing and ethyl cellulose, terpinol are mixed to be dissolved in 2: 1: 8～1: 1: 5 mass ratio and be prepared into the elementary slurry of ZnO in the absolute ethyl alcohol;
C. with the elementary slurry of ZnO uniform spreading on conductive substrates, leave standstill homogenizing 15 minutes, calcined 0.5～1 hour down at 400～800 ℃ then, can obtain ZnO nano particle porous film electrode;
D. draw silica sol and drip the ZnO nano particle porous membrane surface that makes in above-mentioned, left standstill for 10 seconds after rotation apply, up to the combination electrode of the parameter request that obtains required uniform coating;
E. after above-mentioned spin coating is good combination electrode is heat-treated, the SiO that promptly makes 2-ZnO nano particle porous membrane combination electrode.
2. SiO as claimed in claim 1 2The preparation method of the ZnO nano-porous film combination electrode of modifying, it is characterized in that: the content of silica is 10～26wt% in the silica sol.
3. SiO as claimed in claim 1 2The preparation method of the ZnO nano-porous film combination electrode of modifying is characterized in that: the technology of the even glue of spin coating in the rotation coating is in 1000 rev/mins of rotations 5～10 seconds down of low speed, rotated 10～20 seconds down for 3000 rev/mins in high speed.
4. SiO as claimed in claim 1 2The preparation method of the ZnO nano-porous film combination electrode of modifying is characterized in that: the good combination electrode heat treatment temperature of step e. spin coating is in 400～800 ° of C intervals, and heat treatment time is 0.5～1 hour.
CN 201010575239 2010-12-01 2010-12-01 Method for preparing SiO2-modified ZnO nano-porous thin film composite electrode Expired - Fee Related CN102005303B (en)

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CN102480051A (en) * 2011-08-31 2012-05-30 深圳光启高等理工研究院 Preparation method of meta-material dielectric substrate
CN103035410B (en) * 2011-10-08 2018-02-06 中国科学院上海硅酸盐研究所 Dye sensitized optoelectronic converting device and its manufacture method, and metal oxide paste
CN103413755A (en) * 2013-08-27 2013-11-27 北京世纪先承信息安全科技有限公司 Method for preparing monocrystal SiC film with silicon substrate gel lamination pyrolytic reaction method
CN111492529B (en) * 2017-11-28 2022-02-15 江苏经纬知识产权运营有限公司 Preparation method of composite conductive slurry

Citations (3)

* Cited by examiner, † Cited by third party
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CN101162739A (en) * 2007-11-13 2008-04-16 清华大学 ZnO electric pole of dye sensitization solar cell and method for producing the same
CN101354968A (en) * 2008-09-16 2009-01-28 彩虹集团公司 Light anode for dye sensitization solar battery and preparation method thereof
CN101770869A (en) * 2010-02-09 2010-07-07 新奥科技发展有限公司 Method for preparing titanium dioxide films for dye-sensitized solar battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101162739A (en) * 2007-11-13 2008-04-16 清华大学 ZnO electric pole of dye sensitization solar cell and method for producing the same
CN101354968A (en) * 2008-09-16 2009-01-28 彩虹集团公司 Light anode for dye sensitization solar battery and preparation method thereof
CN101770869A (en) * 2010-02-09 2010-07-07 新奥科技发展有限公司 Method for preparing titanium dioxide films for dye-sensitized solar battery

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